Aqueous dye bath composition and process for the dyeing of shaped articles of polyacrylonitrile

ABSTRACT

A PROCESS AND ARTICLE OF MANUFACTURE OBTAINED WHEREIN SHAPED ARTICLES OF POLYACRYLONITRILE OR COPOLYMERS OF ACRYLONITRILE WITH OTHER VINYL COMPOUNDS EXEMPLIFED BY VINYL CHLORIDE AND ACRYLIC ACID ALKYL ESTERS, SAID ARTICLES BEING TREATED WITH A CATONIC DYESTUFF IN A HEATED DYEING COMPOSITION CONTAINING ABOUT 9K-2.5% BY WEIGHT OF THE QUATERNIZATION PRODUCT OF AN ALKENYL-SUCCINIC ACID IMIDAMINE.

United States Patent Office 3,556,715 Patented Jan. 19 1971 U.S. Cl.8-168 4 Claims ABSTRACT OF THE DISCLOSURE A process and article ofmanufacture obtained wherein shaped articles of polyacrylonitrile orcopolymers of acrylonitrile with other vinyl compounds exemplified byvinyl chloride and acrylic acid alkyl esters, said articles beingtreated with a cationic dyestuff in a heated dyeing compositioncontaining about .5-2,5% by weight of the quaternization product of analkenyl-succinic acid imidamine.

The present invention relates to a process for the dyeing of shapedarticles of polyacrylonitrile; more particularly it concerns a processwhich comprises dyeing the shaped articles of polyarylonitrile withcationic dyestuffs in the presence of the quaternisation products ofalkenyl-succinic acid imidamines of the formula in which R represents analkyl radical containing 6 to 22 carbon atoms, and R and R stand,independently of one another, for alkyl radicals containing 1 to 3carbon atoms, while It is a number from 2 to 6'.

The quaternisation products according to the invention can be obtained,for example, by reacting olefines of the formula in which R has the samemeaning as above, with maleic anhydride to give the alkenyl-succinicanhydrides of the formula 1 converting the reaction products withdiamines of the formula R2 (IV) in which R R and n have the same meaningas above,

into the compounds of the Formula I and treating the latter with theconventional quaternising agents.

Examples of olefines of the Formula II include: undecene-(l),dodecene-(4), octadecene-(l), nonadecene- (1) and eicosene-(l), ormixtures thereof; as diamines of the Formula IV there may be used, eg3-dimethyl-aminopropylamine and 6-dimethyl-aminohexylamine, and examplesof quaternising agents are benzyl chloride, chloromethyl-phthalimide anddimethyl sulphate.

The necessary amounts of the quaternisation products can be readilydetermined by preliminary experiments; in general, amounts of 0.5 to2.5%, calculated on the shaped articles of polyacrylonitrile to be dyed,have proved to be sufiicient.

The cationic dyestuffs used for the process of the present invention maybelong to a great variety of groups. Suitable dyestuffs are, forexample, diphenylmethane dyestuffs, triphenylmethane dyestuffs,rhodamine dyestuffs and onium group containing azo or anthraquinonedyestuffs; furthermore thiazine, oxazine, methine and azomethinedyestuffs (cf., e.g., American Dyestuff Reporter, 1954, pages 432 and433).

The shaped articles of polyacrylonitrile can be dyed in usual manner byintroducing the material to be dyed into an aqueous bath heated to about50 to 60 C. and containing a cationic dyestulf, a quaternisation productto be used according to the invention, additions of salts, such assodium acetate or sodium sulphate, as Well as acids, such as acetic acidor formic acid, subsequently increasing the temperature of the dyebathto approximately C. in the course of about 30 minutes, and then keepingthe dyebath at this temperature until the bath is exhausted.Alternatively, the basic dyestuff may subsequently be added to thedyebath, for example, at the time when the temperature of the bath hasrisen to about 60 C. Furthermore, the material to be dyed may bepretreated at a temperature of 40 to 100 C. with a liquor which containsthe customary salts and acids as well as the quaternisation productaccording to the invention, but not yet a dyestufi", only thereafteradding the dyestufl? and carrying out the dyeing at 100 C. Finally, itis also possible to introduce the material to be dyed immediately intothe dyebath heated to approximately 100 C. and containing aquaternisation product according to the invention. With the aid of theprocess according to the invention it is possible to dye a great varietyof shaped articles obtained from polyacrylonitrile, such as cablesheathings, filaments, flocks, combed materials, yarns, woven or knittedfabrics, in an outstanding uniform manner, and this is also possible, incontrast to the quaternary ammonium compounds hitherto used, in thosecases in which shaped articles of polyacrylonitrile are dyed in colourswhich bleed very rapidly.

The term shaped articles made of polyacrylonitrile, comprises in thepresent case also those materials which are produced by also using, incombination with acrylonitrile, other vinyl compounds, such as vinylchloride, vinyl acetate, vinylidene chloride, vinylidene cyanide andacrylic acid alkyl ester.

The following examples serve to illustrate the invention without,however, limiting the scope thereof.

containing, per litre, 0.125 g. of the dyestuff (Colour Index, 2ndedition, No. 51,005), 0.5 g. glacial acetic acid,

3 4 0.5 g. sodium acetate and 0.25 g. of the quaternisation mm. Hg andat an external temperature of at most 70 product of the formula C. Thebrownish yellow, hygroscopic quaternisation prodo l (l HC(CH2)14-m-CH=CH-CH;CHC (1H,

/NCHz-CHzCHz-NCH;N Clorrz-c CH3 ll H o Dyeing is started at 60 C., thetemperature of the bath uct remained as the residue. It can be added tothe dyeis then increased to 98 C. and the bath is kept at boiling l5bath as such or in the form of an aqueous solution.

temperature for about 90 minutes. A pale blue dyeing of We claim:excellent uniformity is obtained. 1. A process for dyeing of shapedarticles made of The quatemisation product used was prepared in thehomopolymers of acrylonitrile or copolymers of acrylonifollowing manner:300 g. olefines having a chain length trile with a vinyl compound,comprising dyeing the shaped of 18 to 20 carbon atoms were heated at 220C. for 4 20 articles with cationic dyestuffs in the presence of anactive hours in a nitrogen atmosphere. The reaction mixture was amountof the quaternization product of an alkenyl-sucsubsequently subjected toa vacuum distillation. When cinic acid imidamine of the formula 202 g.of first runnings had been distilled over at 3 mm. Hg and at atemperature between 140 C. and 188 C., II there were obtained as themain fraction, at 1.4 to 2.2 R CH=CH CH CH C mm. Hg and at a temperatureranging from 237 C. and N(CH2)u-' 242 C., 139 g. alkenyl-succinicanhydride. 60 grams of CHTC this anhydride were heated at 190 C. for 3hours with ll 1 03 g. 3-dimethylamino-propylamine. From this reaction hh in w 1c mixture, unreacted amine and the water formed in the reactionwere then distilled off at 20 mm. Hg. 22.5 grams R i lk l f 6 22 bo t ofthe distillation residue and 10.2 g. N-chloromethyland R2 areindependently d fi d as lk f 1. 3 phthalimide were subsequentlydissolved in 100 ml. methb atoms; d

ylene chloride, the solution was allowed to stand at room i 2 5temperature for 2 days, and the solvent was then distilled off at 20 mm.Hg and at an external temperature T process. of m 1 Wherem the Shapedamcl? of at most 70 C. The brownish yellow hygroscopic E Fpolyaclylommle or a copolymer of acrylom trile with a monomer selectedfrom the group consisting quaternisation product remained as theresidue. It can bfi added to the dyebath as such or in the form of an ofvmyl chloride, vmyl acetate, vmylidene chloride, vmylidene cyanide andacrylic ester.

aqueous soluuon' 40 3. The process of claim 1 wherein R is an alkylradical EXAMPLE 2 of 15-17 carbon atoms; and quaternization is efi'ectedby contacting the imidamine with an active amount of a A fabric ofpolyacrylonitrile fibres is introduced into member selected from thegroup consisting of benzyl a bath having a goods-to-liquor ratio 1:40,heated to 60 chloride, chloromethyl-phthalimide and dirnethyl sulfate.

C. and containing, per litre, 0.125 g. of the cationic dye- 4. Anaqueous dyebath compoistion containing a catstuff obtained bymethylation of 2-chloro-4-nitroionic dyestutf for dyeingpolyacrylonitrile materials and anilineN-ethyl-N-(fl-dimethylaminoethyl)-aniline, 0.5 g. about .52.5% by weightreferred to the weight of the glacial acetic acid, 0.5 g. sodium acetateand 0.2 g. of the articles being dyed, of the quatcrnization product ofquaternisation product of the formula claim 1.

O H30(CH2) 4-1aCH CHCH2CH (3H3 /NCHz-CHzCHgIIl-CHz- Cl CH3 I'll CH3 Thebath is then slowly heated to 98 C. and kept at this References Citedtemperature for about 90 minutes. A pale red dyeing of UNITED STATESPATENTS excellent uniformity is obtained.

The quaternisation product used was prepared as fol- 2986444 5/1961Roliohl et a1 8*177 lows: 45 g. of the distillation residue described inExam- 309869O 7/1963 Gulon 8 84 ple 1 and obtained after the reaction ofalkenyl-succinic GECRGE F. LESMES, Primary Examiner anhydride with3-dimethylamino-propylamine, and 13 g. Q IVES, Assistant Examiner benzylchloride were dissolved 1n ml. methylene chloride, the solution wasallowed to stand at room temperature for 2 days, and the solvent thendistilled off at 20 8-4, 84,172,177;260326.5

